KR960042238A - Uses of cyclic polysaccharide inclusion compounds as charge control agents - Google Patents

Abstract

An inclusion compound comprising 3 to 100 monomeric saccharide units, which is a cyclic-linked polysaccharide formed in its molecular skeleton, and at least one chemical compound contained as a guest compound in the cavity, Triboelectrically or electrokinetically sprayable powders and as charge control agents and charge control agents in powder coatings and electret materials.

Description

Uses of cyclic polysaccharide inclusion compounds as charge control agents

Since this is a trivial issue, I did not include the contents of the text.

Claims (17)

An electrophotographic toner comprising a host compound which contains 3 to 100 monomeric saccharide units and is a cyclic bonded polysaccharide which forms a cavity in its molecular skeleton and an inclusion compound composed of at least one chemical compound contained as a guest compound in the cavity, And as developers, triboelectrically or electrostatically atomizable powders and as charge control agents and charge improving agents in powder coatings and electret materials. The use according to claim 1, wherein the host compound is a 1,4-linked pyranose of the general formula (I) or a 1,6-linked pyranose of the general formula (II). Wherein n ¹ is a number from 6 to 100, n ² is a number from 3 to 100, and R ¹ , R | ² and R < ³ > are, independently of each other, the same or different, hydroxyl; Branched or unbranched, cyclic or branched C ₁ -C ₃₀ -alkoxy; Branched or unbranched, cyclic or branched C ₂ -C 6 alkyl, ₃₀ -alkenoxy, wherein alkoxy and alkenoxy radicals may be partially or fully fluorinated; Unsubstituted -O- aryl (C ₆ -C _30), or 1 to 5 C ₁ -C ₃₀ - alkyl, radical or a C ₁ -C ₃₀ - aryl optionally substituted by a -O- alkoxy radical (C ₆ -C ₃₀ ); _{-O- (C 1 -C | 4)} - alkyl, - (C ₆ -C ₃₀₎ aryl; -OC ₆₀ -C ₇₀ -fullerene; -O- (alkylene (C ₀ -C ₃₀₎ -Y- alkyl _{- (C 1 -C | 30)} ) x, -O- ( aryl (C ₆ -C ₃₀₎ -Y- aryl - (C ₁ - C _{30)) x,} -O- (aryl (C ₆ -C ₃₀₎ -Y- alkyl, _{- (C 6 -C 30))} | _x, -O- (alkylene- (C ₆ -C ₃₀ ) -Y-aryl- (C ₆ -C ₃₀ ) -alkyl (C ₀ -C ₄ )) _x wherein x is from 1 to 30, And Y is a chemical bond, O, S, SO ₂ , PR ⁴ , PR ⁴ ₃ , Si, SiR ⁴ ₂ or NR ⁴ wherein the radical R ⁴ is hydrogen, C ₁ -C ₄ -alkyl Or C ₁ -C ₄ -alkoxy; Radical-O-COR ⁶ wherein R ⁶ is OH, saturated or unsaturated, branched or unbranched, cyclic or in the ring (C ₁ -C ₁₈ -alkyl, partially fluorinated or perfluorinated ((C ₁ - . C ₁₈₎ - alkyl, phenyl or (C ₁ -C ₁₈₎ - alkyl-phenyl; radical -O-PR ₂ ⁷ or -O-PR ₂ ⁷ {wherein R ⁷ is hydrogen, methyl, ethyl, propyl, butyl vinyl, allyl, isopropyl, isobutyl, neopentyl, t- butyl, cyclohexyl, cyclopentyl, phenyl, tolyl, benzyl, partly fluorinated or perfluorinated alkyl, - (C ₁ -C _18), and O , OH, S, and NR ⁸ ₂ (wherein, R ⁸ is hydrogen, C ₁ -C ₈ - alkyl or phenyl)}; radical -O-SO ₂ R ⁹ (wherein, R ⁹ is methyl, ethyl, propyl, butyl (C ₁ -C ₁₈ ), O (C ₁ -C ₁₈ ), partially fluorinated or perfluorinated alkyl, (C ₁ -C ₁₈ ) alkyl, (C ₁ -C ₁₈ ) alkenyl such as vinyl, allyl, isopropyl, isobutyl, neopentyl, t- butyl, cyclohexyl, cyclopentyl, phenyl, , OR ⁸ , S, or NR ₂ ⁸ A radical -O-SiR ¹⁰ ₃ wherein R ¹⁰ is selected from the group consisting of methyl, ethyl, propyl, butyl, vinyl, allyl, isopropyl, isobutyl, neopentyl, t- butyl, cyclohexyl, cyclopentyl, O-BR ¹¹ ₃ wherein R ¹¹ is selected from the group consisting of methyl (C ₁ -C ₁₈ ), O, OR ⁸ , S, or NR ₂ ⁸ ; , ethyl, propyl, butyl, vinyl, allyl, isopropyl, isobutyl, neopentyl, t- butyl, cyclohexyl, cyclopentyl, phenyl, tolyl, flower part, by fluorine or perfluorinated alkyl (C ₁ -C ₁₈ ), O, OH, oR ^8, S or a NR ₂ ^8);. the formula -NH _2, -NHR ^12, or amino radical -NR ¹² ₂ (wherein, R ¹² are respectively the same or different and 1 to 3 A C ₁ -C ₃₀ aliphatic, C ₇ -C ₆₀ araliphatic or C ₆ -C ₃₀ aromatic hydrocarbon radical which may be interrupted by two or more heteroatoms N, O and / or S; Perfluorinated or partially fluorinated alkyl (C ₁ -C _18); Or the nitrogen atom of the amino radical is a saturated or unsaturated, aromatic or non-aromatic 5 to 12 membered ring which may contain further heteroatoms selected from nitrogen, oxygen, sulfur or a combination thereof and which may be fused together or bridged to a further ring system. 7 < / RTI > ring system; Or ammonium radical -NR ¹² ₄ ^- A ^- , wherein A ^- is an inorganic or organic anion; Or an azide radical -N ₃ ; Or the radicals R ¹ and R ² or R ² and R ³ together are formula In the form a ring system, and X is _{^{-CH 2 R 1, CH 2- NO}} 2, -CH 2 -Hal ( wherein, Hal is a _{halogen.), -CH 2 OH, -CH} 2 OCH 3, -CH 2 OCO (C ₁ -C ₄₎ alkyl, -CH ₂ -O-SiR | ₃ ^4, -CH ₂ -O- _{trityl, -COOH-, -COO- (C 1 -C} 4) _{alkyl, -CH 2 -O-SO 2 -} (C 1 -C 4) - alkyl or -CH ₂ -O-SO ₂ -C ₆ H ₄ - (C ₁ -C ₄ ) -alkyl. The compound according to claim 2, wherein n ¹ is a number of 6 to 80, preferably 6 to 60, n ² is a number of 3 to 60, and R ¹ , R ² and R ³ are each independently -O- ( C ₂ -C ₃ -alkylene-O) _x -R ⁵ wherein R ⁵ is hydrogen, C ₁ -C ₄ -alkyl, acetyl, benzoyl or naphthoyl, and x is a number from 1 to 30; -PO (OH ₂ ) or -PO- (OC ₆ CH ₅ ) ₂ . 4. The method according to claim 2 or 3, wherein the R^One, R²And R³Independently of one another are selected from the group consisting of hydroxyl, methoxy, ethoxy, propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, t-butyloxy, vinyloxy, allyloxy, phenoxy,₃, -O- (CH₂CH₂-O)_x-R⁵, -O-COR¹³(Wherein R¹³C_One-C₈- alkyl, phenyl or C_One-C₈-Alkyl-phenyl) or an ammonium group -NR < RTI ID = 0.0 >¹⁴R¹⁵(Wherein R¹⁴And R¹⁵Are independently of each other hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, allyl, vinyl, phenyl, benzyl or tolyl or the nitrogen atoms are piperidyl, morpholinyl, Lt; / RTI > or quinolinium ring system); Or an ammonium group -N HR¹⁴R¹⁵A '(Where A ') Is a borate, sulfate, chloride, bromide, nitrate, cyanide, phosphate, carbonate, acetate or alcoholate anion) and X is -CH₂Cl, -CH₂Br, -COO-CH₃, -CH₂-O-Si (-CH₃)₃, -CH₂-O-SO₂-CH₃Or -CH₂-O-SO₂-C₆H₄CH₃For use. 5. A compound according to any one of claims 2 to 4, wherein the host compound is a 1,4-linked cyclodextrin of the general formula (I) wherein R ¹ and R ² are each OH, X is CH ₂ OH, and n < ¹ > is a number from 6 to 8. 6. The compound according to any one of claims 1 to 5, wherein the guest compound is branched or unbranched, saturated or unsaturated, substituted or unsubstituted, aromatic or aliphatic, cyclic or straight chain alkoxy; Branched or unbranched, saturated or unsaturated, substituted or unsubstituted, aromatic or aliphatic, cyclic or straight chain ketone; Branched or unbranched, saturated or unsaturated, substituted or unsubstituted, aromatic or aliphatic, cyclic or straight chain aldehyde; Branched or unbranched, saturated or unsaturated, substituted or unsubstituted, aromatic or aliphatic, cyclic or straight chain carboxylic acid; Branched or unbranched, saturated or unsaturated, substituted or unsubstituted, aromatic or aliphatic, cyclic or straight chain polyalcohol; Substituted or unsubstituted quinone; Branched or unbranched, saturated or unsaturated, substituted or unsubstituted sugar; Branched or unbranched, saturated or unsaturated, substituted or unsubstituted, aromatic or aliphatic, cyclic or straight chain ether; Branched or unbranched, saturated or unsaturated, substituted or unsubstituted, aromatic or aliphatic, cyclic or linear chain thiol; Branched or unbranched, saturated or unsaturated, substituted or unsubstituted, aromatic or aliphatic, cyclic or straight chain cyano compound; Aromatic or aliphatic nitro compounds; Primary, secondary or tertiary amines NR ₃ (wherein, R is H, OH, a halogen or a branched or unbranched, saturated or unsaturated, cyclic substituted or unsubstituted, aromatic or aliphatic, or a straight-chain hydrocarbon ladder kill) ; Organometallic compounds such as ferrocene or metal alkyl; Boron compounds BR ₃ and BR ₄ ^- , wherein R is as defined above; Silicon compound SiR ₄ (wherein R is as defined above); Phosphorus compounds PR ' ₃ , PR' ₅ , or PR ' ₆ , wherein R' is H, O, S, OH, halogen or an organic radical; Sulfur compounds SR ' ₂ , SR' ₃ , -SO ₃ , SR ' ₄ (wherein R' is as defined above); Ammonium compound NR ' ₄ , wherein R is as defined above; Inorganic cations such as monovalent, divalent, trivalent or tetravalent metal cations; A monovalent or divalent organic anion, preferably a carboxylate, phenolate, thiolate or alcoholate; Or an inorganic anion, or a salt of one of the above-mentioned cations with one of the above-mentioned organic or inorganic anions. 7. The process of any one of claims 1 to 6 wherein the guest compound is selected from the group consisting of C ₁ -C ₃₀ aliphatic, C ₂ -C ₃₀ olefinically unsaturated and C ₃ -C ₃₀ alicyclic alcohols; C ₃ -C | ₃₀ aliphatic, C ₄ -C ₃₀ olefinically unsaturated, C ₄ -C ₃₀ alicyclic and C ₈ -C ₃₀ aromatic ketones; C ₁ -C? ₃₀ aliphatic, C ₃ -C ₃₀ olefinically unsaturated, C ₄ -C ₃₀ group, and a substituted C ₇ -C ₃₀ aromatic aldehyde; C ₁ -C? ₃₀ aliphatic, C ₃ -C ₃₀ olefinic unsaturation, C ₄ -C ₃₀ alicyclic and C ₇ -C ₃₀ aromatic carboxylic acids; C ₂ -C | ₃₀ aliphatic, C ₄ -C ₃₀ olefinically unsaturated or C ₈ -C ₃₀ aromatic dicarboxylic acid; C ₂ -C ₆ alkyl group having 2 to 10 hydroxyl groups ₃₀ aliphatic, C ₃ -C ₃₀ olefinically unsaturated, C ₃ -C ₃₀ alicyclic and C ₆ -C | ₃₀ aromatic polyalcohol; C ₆ -C ₃₀ hydroxy aromatic compounds; Quarternary alicyclic groups and aromatic ethers having 6 to 30 carbon atoms; Polyethers containing from 3 to 100 ethoxy and / or propoxy units; NH _3, mono - (C ₁ -C ₁₈₎ - alkyl, di - (C ₁ -C ₁₈₎ - alkyl and tri _{- (C 1 -C | 18)} - alkyl-amines, a nitrogen-containing heterocycle; amino acid; Alkali metal and alkaline earth metal cations, Zn ²⁺ , Mn ²⁺ , Co ²⁺ , Fe | ³⁺ and Al ³⁺ , NO ₃ ^- , OH ^- , HSO ₄ ^- , SO ₄ ^2- , HSO | ₃ ^- , SO ₃ ^2- , S ₂ ^- , S ₂ O ₃ ^2- , HCO ₃ ^- , CO ₃ ^2- , H ₂ PO ₄ ^- , HPO ₄ ^2- PO ₄ ³ , CN ^- , CF ₃ SO _{3 ^{-, CF 3 COO -, F}} -, Cl -, Br -, I -, PF 6 -, zinc tetra-cyanate, perchlorate, SiF ₆ ^2-, tetrafluoroborate, tetraphenylborate; Saturated or unsaturated aliphatic or alicyclic or aromatic carboxylates or sulfonates; And disulfopyrrolidinium betaines of the general formula (IV). (C ₁ -C ₅ ) or alkoxy- (C ₁ -C ₅ ) radicals, polyoxyalkylene radicals, preferably polyoxyethylene or polyoxyalkylene radicals, in which R ₁ 'and R ₂ ' (C ₁ -C ₅ ) -O) _n -R wherein R is a hydrogen atom or an alkyl (C ₁ -C ₄ ) radical and n is an integer from 1 to 10 And X and Y are each alkylene (C ₁ -C ₅ ). The process according to any one of claims 1 to 7, wherein the cyclic bonded polysaccharide (host compound) comprises in each case the same or an enantiomeric saccharide unit or an enantiomeric mixture of the said unit, wherein R ¹ , R < ² >, R < ³ > and X have the same meanings in each case). 9. The use according to any one of claims 1 to 8, wherein a mixture or blend of inclusion compounds having the same or different guest compounds is used. An electrophotographic toner comprising a conventional toner binder and 0.01 to 50% by weight, preferably 0.5 to 20% by weight, of at least one inclusion compound according to any one of claims 1 to 9. The method of producing an electrophotographic toner as claimed in claim 10, wherein the inclusion compound is homogeneously incorporated into the toner binder. A polyester resin or an acrylic resin containing an epoxy, a carboxyl group or a hydroxyl group, or a mixture of these resins and 0.01 to 50% by weight of at least one inclusion compound according to any one of claims 1 to 9, 0.5 to 20% by weight. A process for producing a powder or powder coating as claimed in claim 12, wherein the inclusion compound is uniformly incorporated into the resin. A host compound which is a cyclic bonded polysaccharide which contains 3 to 100 monomeric saccharide units and forms a cavity in its molecular framework, and a host compound having a solid particle size of 0.1 to 1000 탆, preferably 0.5 to 100 탆, An inclusion compound composed of at least one compound contained in the cavity as a guest compound, having a water content of 0.1 to 20% as measured by the Fischer method and a thermal stability of 200 DEG C or more. The inclusion compound according to claim 14, wherein the host compound is as defined in any one of claims 2 to 5, and the guest compound is as defined in claim 6 or 7. 15. The method of claim 14 or claim 15, wherein the host compound is as defined in claim 5, wherein the guest compound LiCl, ZnCl _2, SrCl _2, octadecyl-3- (3,5 - t- butyl-4-hydroxy hydroxyphenyl) _{-propionate, Na 2 CO 3, NaBF 4} , Zn (NO 3) 2, CdCl 2, FeSO 4, oxalic _{acid, NaB (C 6 H 5)} 4, KNO 3, coconut alkyl dimethyl benzyl ammonium chloride, But are not limited to, salicylic acid, stearic acid, MnSO ₄ , triphenylamine, sodium trifluoromethanesulfonate, CH ₃ COONa, p-benzoquinone, anthracene, 2,5- Methylphosphonium chloride, ferrocene, KPF ₆ , K ₂ Ca (NO ₃ ) ₂ , CaSO ₄ , AL (NO ₃ ) ₃ , propionic acid, glycol bis [3,3-bis (4'-hydroxy-3'-t-butylphenyl) butanoate], pentaerythritol tetrakis [3,5- -Hydroxyphenylpropionate], β, β'-thiodi (lauryl propionate), β, β'-thiodi (stearyl propionate), dioctadecyl disulfide, tris (2,4- t-butylphenyl) phosphite, C ₁₂ / C ₁₄ -alkyltrimethylammonium chloride, benzoic acid, didecyldimethylammonium chloride, didecylmethylalkoxyammonium propionate, poly (diallyldimethylammonium chloride), K ₂ CO ₃ , (Trihydroperfluoroalkene) -N, N, N-trialkylammonium methosulfate, 2,4,5,2'3 ', 4-hexahydroxybenzophenone, 2,4,6-tri Hydroxybenzoic acid or 1,1,1-trihydroxymethyl ethane. The process according to any one of claims 14 to 16, wherein the cyclic bonded polysaccharide is reacted with a guest compound at a pH of 7 to 14, preferably 8 to 12, and the resulting inclusion compound is spray dried, dried and milled ≪ / RTI > ※ Note: It is disclosed by the contents of the first application.